Copper(II)-catalyzed reactions of activated aromatics

The catalytic reaction of cis-bisglycinato copper(II) monohydrate in the pr esence of hydrogen peroxide:de leads to hydroxylation of phenol to give cat echol and hydroquinone (1:1.2 ratio) in good yield. 2,6-Dimethylphenol can be hydroxylated by hydrogen peroxide and a catalytic amount of cis-bisglyci nato copper(II) monohydrate to give an aggregate of 1,4-dihydroxy-2,6-dimet hylbenzene and 2,6-dimethylphenol. A similar reaction of o-cresol gives 2,5 -dihydroxytoluene. The reactivity of cis-bisglycinato copper(II) monohydrat e in hydrogen peroxide with o-cresol is 4.5 times faster than that of a sim ilar reaction by trans-bisglycinato copper(II) monohydrate. A catalytic rea ction of cis-bisglycinato copper(II) monohydrate with aniline in aqueous hy drogen peroxide gives polyanilines in the form of pernigraniline with diffe rent amounts of Cu(OH)(2) attached to them. The two major components of pol yanilines obtained have M-n values of 1040 and 1500, respectively. Resistan ce of films of these polyanilines increases with temperatures from 40 degre es C to a maximum value at 103 degrees C and then decreases in the region o f 103-150 degrees C, showing the property of a thermoelectric switch. The a ggregate prepared from hydroxylation of 2,6-dimethylphenol shows a similar property in the region of 30-180 degrees C.